Reforming with a heteropoly acid catalyst in the presence of water



May l2, 1959 J. TURKEVICH REFORMING WITH A HETEROPOLY ACID CATALYST y INTHE PRESENCE OF' WATER Filed Dec. 5, 1952 United StatesPatentD REFORMINGWITH A HETEROPOLY ACID CATA- LYST IN THE PRESENCE F WATER John Tnrkevch,Princeton, NJ., assignor to The M. W. Kellogg Company, Jersey City, NJ.,a corporation of Delaware Application December 5, 1952, Serial No.324,182

23 Claims. (Cl. 208-134) This invention relates to an improved reformingprocess, and more particularly pertains to an improved reforming processfor light hydrocarbon oils. in which a small amount of water is employedfor the reforming reaction.

At present, considerable emphasis is being placed on the fluidhydroforming process in which a molybdenum oxide type of catalyst isemployed for commercial application. This process has many advantagesover a fixed bed type of operation in which a platinum catalyst isutilized, however, it was found that the molybdena type of catalyst doesnot produce equivalent yields of reformed liquid product. After carefulinvestigation, it was found that the yields in a fluid hydroformingprocess employing a molybdena type of catalyst could be improvedsigniiicantly by employing a small amount of water in the reaction zone.appraisal of this more recent development, it was determined that aplatinum catalyst still gave a higher yield of reformed liquid producton an equivalent octane basis than that obtained with the use of a smallamount of water in the uid hydroforming process. Further investigationhas been carried out in an effort to find methods of improving the fluidhydroforming process so as to increase the yields of the high octaneproduct. By means of this invention, it is proposed to employ adifferent type of catalyst in the reforming operation with a smallamount of water in the reaction cycle to obtain significantly higheryields.

ln accordance with the present invention, light hydrocarbon oils arereformed by the process which comprises contacting a heteropoly acidcatalyst with a light hydrocarbon oil under suitable reformingconditions including the use of a small -amount of water.

The heteropoly acid catalyst may be optionally pretreated with ahydrogen containing gas, with or without the use of small amounts ofwater, at an elevated temperature prior to use in the reformingoperation. This treatment can be effected in the presence of a smallamount of water, generally, in the amount of about 0.1 to about l5 molpercent based on the-quantity of hydrogen employed, more usually, about0.5 or 1.0 to about 6.0 mol percent of water on the same basis. Undersome conditions, it is preferred to employ about 2 to about 6 molpercent of water, based on the hydrogen charged to the pretreating zone.The hydrogen containing gas employed for this purpose can be purehydrogen or a gas containing hydrogen in the amount of about 35 to about85% by volume. Thispretreatment -with a hydrogen containing gas isconducted at an elevated temperature in the range of about 750 to about1200 F., more usually, about 875 to about ll00 F. In some cases. it isdesirable to pretreat at a temperature of about 930 to about l000 F. Atthe elevated temperature, the pretreatment can be conducted atatmospheric or superatmospheric pressure, eg., about 50 to about 1000p.s.i.g. The rate of hydrogen containing gas employed for thispretreatment is measured on a hydrogen basis, and it As a result of acareful y ice 2 involves about l to about 400 standard cubic feet ofhydrogen per hour. per pound of heteropolyacid oatalyst, preferablyabout 2 to about 100 standard cubic feet of hydrogen per hour per poundof heteropoly acid catalyst. The hydrogen is measured on the basis ofstandard conditions which involve a pressure of 760 mm. and atemperature of 60 F. The reforming process can be practiced as either aliuid or non-fluid operation involving a fixed or moving bed system.Consequently, in the pretreatment of the heteropoly acid catalyst with ahydrogen containing gas, the catalyst can be in the form of lumps,granules, pellets or finely divided particles. In the case of a fluidsystem, it is contemplated in the pretreatment to employ an upwardpassage of gaseous materials including hydrogen through a mass of finelydivided catalyst at a superficial linear gas velocity of about 0.1 toabout 50 feet per second, moreusually, about 0.1 to about 6 feet persecond, and preferably, on a commercial scale, a superficial linear gasvelocity of about l to about 2.5 feet per second. The period oftreatment may vary considerably depending upon the severity ofconditions employed in this operation. Gren-l erally, the pretreatmentoperation is conducted for a period of about 0.05 to about 10 hours,more usually, about 0.2 to about 2 hours. The conditions specified abovecan be used for a pretreatment involving water as well as one in whichthe hydrogen containing gas is employed in a substantially anhydrouscondition. lt should be understood, however, that the pretreatmentinvolving a small amount of water is preferred overv the operationinvolving substantially anhydrous conditions by virtue of the superiorresults obtained thereby. Usually, the water required for thepretreatment of the catalyst is added with the hydrogen containing gas.This procedure can be varied by injecting the water or vapor thereofinto the mass of catalyst after regeneration as a separate stream; or inthe case of a moving bed system the steam or water is fed directly intothe catalyst stream which is flowing from the regenerator to thepretreating vessel or zone. In some cases, the reducing atmosphereprevailing in the reformingzone is suiciently effective so that littleor no benefits are derived from a separate treatment in order tocondition the catalyst.

The physical form of the catalyst involved in the pretreatment operationwill be determined by the type of system which is being used for thereforming'operation. As previously indicated, the catalyst may be usedin the form of lumps, granules, pellets or finely divided material. Inalixed bed system, it is desirable to pretreat` the catalyst, after ithas been regenerated by means of an oxygen containing gas, withouttransferring the catalyst from the processing vessel. In effect, thecycles of operation involve `a reaction phase, regeneration phase andthen a pretreatment phase, with or without suitable purging atappropriate intervals with steam, hydrogen, etc., during the completeoperation. In a moving bed system, it is preferred to employ a separatepretreating vessel for the purpose of conditioning the catalyst beforevpresent invention is a light hydrocarbon oil and includes,

` for example, gasoline, naphtha and kerosene.

y naphtha fraction, it is preferred to employ a naphtha a having aninitial boiling point of about 100 to about 250 F. and an end point ofabout 350' to about 450 F. Generally, the light hydrocarbon oil to bereformed has a Watson characterizationfactor of about 11.50 to about1220i The feed material' can be one which is a straight run or virginstock, a cracked stock which is derived'from a thermal or catalyticcracking operation, or a mixture or a blend of straight run and crackedstocks.v Accordingly, the octane number of the feed material can be atleast CFRR clear, or more usually, about 20 to about 70 CFRR clearandthe olefin content ofthe oil can vary from abouti 0. to about 30 molpercent. This light hydrocarbon oilr can be derived from any. type. ofcrude. oil, consequently, it can contain sulfur. in the amount ofO toabout3.0 percent by weight. The light.hydrocarboncilisreformed underconditions wljchcaninvolve the. net. consumption or. net. productionoffhydrogen. A systemA involvingV the. netproduction of'h'ydrogenis.commonly referred. to, as hydroforming, and'it isoperated,undersuchtconditions thatthe quantity offhydrogen. producedissuicient. to sustainthe process without, need'for extraneous hydrogen.Generally, for the reforming of light hydrocarbony oils, a temperatureofabout 750 to about .1100'o F. is employed. At this temperature, thepressure of the. operation is generally maintained at about 25 to about1000 p.s.i.g. The quantity of oil processed relative to the. amount ofcatalyst employed is measured in termsof tbe-weight space velocity, thatis, the pounds of oilv feed on an hourly basis charged to they reactionzone per pound of catalyst which is. present therein. The Weight spacevelocity can vary from about 0.05 to about 10. The quantity of. hydrogenwhich is added to the process is usually measured in terms of thestandard cubic feet of hydrogen (measured at 60 F. and 760 mm.) perbarrel of oil feed charged to the reforming operation (l barrel=42gallons). On this basis, the hydrogen rate is about 500 to about 20,000s.c.f.b. Another method ofindieating the quantity of hydrogen which canbe present during the reforming operation is by means vof hydrogenpartial pressure. In this regard, the hydrogen partial pressure is aboutto about 950 p.s.i.a. in the reaction zone, based on inlet conditions.

, In a` hydroforming operation, the reaction conditions fall within theranges specified hereinabove, however, they are selectedfonthe basisofobtaining a net production. of hydrogen. Accordingly, a preferredhydrofrming process involves a temperature. of about 850 to about 1050"F.; a pressure of about 50 to about 500 p.s.i.g,; a weight spacevelocity of'about 0.1 to about 3;' a hydrogen rate of about 1000 to 7500s.c.f.b. and a hydrogen partial'pressure of yat least about 25 p.s.i.g.and up -to the point at which hydrogen is consumed.

The reforming of the light hydrocarbon oil is effected with the useof asmall amount of water. Apparently, the`pretreatment ofk catalyst withhydrogen containing a small amount of Water imparts sufficient desiredactivity tothe catalyst to make `possible the'production ofsignificantlyV higher yields of -reformed liquid product of highanti-knock quality. I-Ie'nce,` it is preferred in a reformingkoperationto employ a small amount of Water during the operation toinsure the production of higher yields of reformed liquid product ofhigh octane quality. Accordingly, it is contemplatedreforminglight hydrocarbonoilsin the presence of about 0.1 to about 'l0 molfpercent kofwater, preferably about'0-.25 to about 5 molpercent 1of -water, basedonthe amountl of hydrogen which is added to the reforming zone. Undersomeconditions-,' it is desirableY to add about 0.5 to about 2.5mol'fpercent ofwater, basedonhydrogen. The'vvater employed forthispurpose can be added` tothe hydrogen containing gasstrearnl'whichis-charged'to thereaction zone; and/Critican beladded intthe formbof aliquid to theloilvfeed and/or it can beadded directly-to the Cilreforming zone.l In-` any mannen of addition of.A the '(5 water, it iscontemplated measuring the quantity thereof on the basis of the amountof hydrogen which is added to the reforming stepg.

Due to the reforming operation, the heteropoly acid catalyst becomescontaminated with carbonaceous material which lowers its. catalyticactivity undesirably. Hence, the catalyst is subjectedl to aregeneration treatment` which -involves contacting thersam'e' with'.a'nnox'ygen containing-gas, exg., oxygernair.; .diluted air having aboutl to about 10% oxygen by volume, etc., at a temperature of about600 toabout.12`50` F.,.preferablyy about 950 F. to about 1150 F Theregeneration is effected at atmospheric pressure or an elevated pressureof about 25 to Pabout '10'00"'p.s:-i.g. Prior toregeneratiomthe-catalyst usually contains aboutt0.1 to. about-.5.0% by weight ofcarbonaceous material, and due to regeneration the carbonaceous materialcontent is reduced to zero content or up toA about 0.5% by weight. It isdesirable to remove asmuchcarbonaceous material as is economical,because possibly ysuchmaterial deposited on the catalyst may undesirablytend to cover the active centers of the heteropoly acid, and thus.renderthe catalyst less eiective yfor the reforming operation. In such a case,the ideal situation may be to burn olf all the carbonaceous materialdeposited on the catalyst.

It is preferred to regenerate the catalyst at superatmospheric pressurerather than atmospheric pressure. In this regard, it is preferred toconduct the regeneration stepwith an oxygen partial pressure of at leastabout 5 p.s.i.a., usually about 6 to about 200 p.s.i.a. A possibleexplanation is that severe regeneration conditions elect the morecomplete removal of deposits which are adverse to catalyst activity.

The reforming operation can be accomplished using a uid or non-fluidtechnique, involvingv either a xed bed orA a moving bed. system. In thecase of a fixed bed operation, at least two processing vessels areemployed in order that-while one vessel is undergoing regenerationand/or pretreatment, the other vessel is processing the lighthydrocarbon oil to be reformed. In the commercial operations of presentday, usually four processingvesselsare employed; This is also suitablein thev present invention, because it provides for larger quantitiesY ofmaterial to be reformed. Normally, in a xed'bed system, the reactioncycle takes about 0.25 to about 8 hours, the regeneration takes about0.25 to about 8 hours and the pretreatingoperation can require about 0.1to about-12.0 hours. In a fluid-moving bed system, the finely-divided..catalytic material has a particle size in the range of .about 0 toyabout 250 microns, more usually, about 10 to about 100 microns. Themass of finely divided'material is uidized by the upward ow of gaseousor vapormaterials therethrough which have a superficial linear velocityof about 0.1 to about 500 feet per second, more usually, about 0.1 -toabout 6 feet per second. In commercial operations, it is preferred toemploy a superflcial linear gasvelocity of about 0.75 to about 2 feetper second. These-linear gas velocities can exist in any of theprocessingvessels, namely, the reactor, the regenerator,.the pretreatingvessel and the transfer lines between vessels. Furthermore, the speciedlinear gas velocities can provide either a lean or dense phase ofuidfmass; Usually, it is preferred to employ a dense phase, becauseit.yprovides a more` intimate contact be tween the gas-iaud/or'vvapor and.the catalyst particles'. Theirrelative rates'of'catalyst beingcirculated and the oil being.l charged to. the reaction zone is usuallytermed the catalystfto oil ratio, on a weight basis. Generally, inamoving bed system, thecatalyst to oilratio is about 0.051to yabout 20.For'commercial operations, it is preferred to employ a vcatalyst to oilratio of about 0.5 to about 5.0.

In thepractice of this invention, it may be desirable that theheteropoly acidifcatalyst, whether it is pretreated or pre-reduced.:under;` the conditions. specified herein.-

above or not, be contacted with the oil charge for a period not greaterthan about 2 hours. In a fixed bed system, this condition is measured asthe reaction cycle or period; whereas in a moving bed system, it is thecatalyst residence time in the reaction zone. For the purpose of thisspecification and the appended claims, catalyst processing time isintended to mean the length of time catalyst is contacted with oil priorto being regenerated or otherwise discontinued from use, and this factoris measured as the reaction cycle or period in a fixed bed and thecatalyst residence time in the reaction zone in a moving bed system. Theheteropoly acid which is employed as catalyst in the present inventionis one having at least two different acid forming elements united in theacid functional group. Gne of the acid forming elements is termed, forthe purpose of this speciiication and the appended claims, as thecentral acid forming element, by reason that, generally, another one ormore outer acid forming elements are bound thereto in the ratio of about3-12 to 1 of outer acid forming element or elements to central acidforming element or elements, more desirably about 12 to 1 on a similarbasis. For example, the ratio of outer acid forming element to centralacid forming element occurs in four main classes having ratios of l2, 9,6 and 3 to l. The same combination of different elements may occur inmore than one class. regarded as those which are attached to the centralacid forming element of the acid forming functional group' inpredominant number. ment is any element which is at least trivalent andis capable of forming an oxygen containing compound which has acidicproperties, and/or an analogous thio compound of acidic properties inwhich all or part of the oxygen atoms are replaced by sulfur. The outeracid forming elements are molybdenum, chromium, tungsten and vanadium.Many of the central acid Iforming elements can be selected from groupsVA and VLA; Whereas the outer acid forming elements can be chosen fromgroups VB and VIB of the periodic table. It is also contemplatedemploying heteropoly acids in which more than one outer acid formingelement is present in the said functional group, as well as more thanone central acid forming element is present therein. The central acidforming elements are, for example, phosphorus, germanium, tellurium,arsenic, aluminum, boron, silicon, manganese, cobalt, rhodium, chromium,selenium, iodine, platinum, antimony, etc. Specific examples of theheteropoly acids are, for example, molybdenum acid iodate,

.wherein X is l to 70 and M is a trivalent element selected from Al, Cr,Fe, Co, Mn or Rh; ammonium acid salt of aluminum molybdate,(NH4)3H6[Al(MoO4)6] 7H2Og molybdenum acid titanate, TiO2-12M0O3-22H2O;molybdenum acid germanate, GeO2-12M0O3-32H2O; molybdenum acid vanadate,V205- 8M0O3'5H2O; ammonium acid salt of thiovanadate-thiomolybdate,

(NH4)5H3[H2(MoS4)4(VS3)2] -10H2O ammonium acid salt of nickelousmolybdate,

(Nr-1,),HrNi Moo,),i -5H,o

ammonium acid salt of cupric molybdate,

(NH4)4,H6[Cu(MoO4)6] -5H2O ammonium salt of ferrie molybdate,

(NH4)3Hs[Fe(MoO4)6] 7H2O ammonium salt of rhodium molybdate,

(NH4)3H5[Rh(MoO4)5l 7H3O The outer acid forming elements will be- Thecentral acid forming elemolybdenum acid platinate, PtO2'l0MoO3'XH2O;chromium racid iodate, 2CrO3-I2O5'5H2O; ammonium acid salt ofphosphovanadate, (NH4)5H2[P(V2O6)6] 21H0; silicomolybdic acid,H4[SiMo12O40]Xl-IZO, wherein X can be 5 to 29; phosphomolybdic acid,

phosphotungstic acid, P205-24WO3-63H2O; silicomolybdic acid,SiO2-12M0O3-32H2O; silicotungstic acid,

SiOgl2MoO3 32H20 borotungstic acid, B2O324WO3-65H2O; aluminomolybdicacid, H'10[Al(MoO4)6]-10H2O; and periodotungstic acid, I20712WO3-11H2O.The heteropoly acids can be derived from the corresponding ammoniumsalts under reaction conditions, consequently, such salts can be used asprecursor materials for the purpose of this invention. Furthermore, itshould be understood, for the purpose of this specification and theappended claims, that the term heteropoly acid is intended to includethe use of those materials which will, under reaction conditions,convert to the active acid form. The heteropoly acids are generally inthe hydrated form, however, it should be understood that these acids areuseful in any state of hydration, although the higher hydrates are moresatisfactory by reason that usually such acids contain high ratios ofouter acid forming element to central acid forming element.

It was found by means of experimental work that the heteropoly acids areexceptionally better as catalysts for reforming of light hydrocarbonoils, which includes, mainly, dehydrogenation, cyclization andisomerization reactions, when used with a small amount of Water in thereforming zone, than molybdenum oxide catalysts under comparableoperating conditions. It appears that the high acidity of the heteropolyacids is highly desirable for reforming reactions, however, since thecatalystis employed in the presence of hydrogen or reducing conditions,there is the danger of the catalyst losing its potency, unless somemeasure is taken to preserve the same. Quite unexpectedly, the use of asmall quantity of water produced exceptional reforming results, whichappears to lend support to the theory that the water prevents thereducing atmosphere from destroying the heteropoly acid. On the basis ofthis theory, it appears that the highly basic heteropoly acids, whichalso tend to be highly hydrated, are excellent catalysts. This propertycan also be expressed in terms of the ratio of outer acid element tocentral acid forming element. It is desirable therefore, to employ thoseheteropoly acids which are at least heptabasic, although the dibasic,tribasic, tetrabasic, pentabasic acids, etc., can be used with varyingdegrees of effectiveness. Accordingly, those acids having about O toabout 63 or 70molecules of water of hydration, more usually, about 3 toabout 30 molecules of water of hydration are employed herein. Thesolubility of heteropoly acids in organic solvents indicates the strongaffinity of these compounds for hydrocarbon groups, It should beunderstood that the above explanation, based on the acidity of theheteropoly acids, is merely advanced as a theory, and I do not intend tobe bound thereby.

The heteropoly acid or mixtures thereof can be used alone, or they aresupported on carrier materials, such as for example, zinc spinel,alumina, silica, magnesia, titania, zirconia, silica-alumina,alumina-magnesia, alumina-titania, pumice, fullers earth, kieselguhr,bentonite clays, SuperliltroL bauxite, alumina-thoria, charcoal, etc.Any support or carrier material may be useful for the catalyst, providedit does not catalyze the undesired reactions to any great extent.Generally, about .5 to about 50% by weight, preferably about 4 to about20% by weight, of heteropoly acid or mixtures thereof are employed,based on the total catalyst. It is desirable to add a small amount ofsilica, i.e., about 0.1 to about 75,- 12% by weight, based on the totalcatalyst, in order toteuhance catalyst: stability at elevatedtemperatures,par-k ticularly inthe caseotusingalumina as asupport. The.alumina can be in the-gel. or activatedfvform as veither etaorgamma-aluminaor.l mixtures of the. two.

Alumina is an excellent supportmaterial for the catalyst of thepresentinvention. Alumina can be prepared by a variety of methods andall ofthese are satisfactory for the purposes; of. this invention.. Inthe preparation of alumina, aluminum; Water; an acid',. such. as. forex.- ample, formic acid, acetic acid or hydrochloric acid; and mercuryor mercuric oxide are reacted under suitable conditionsY andproportionsto produce ahydrous alumina or alumina sol. The alumina solisthcntreatedwith an alkaline reagent, eg., ammonium hydroX-ide,-in.order to effect a gelation. with. an alkaline reagent, itv isdesirable; to adjust .the pH to a value betweenabout to about- 12.. Thealumina can also be prepared by reactingaluminum,.Water: and mercury ormercuric` oxide .at an elevatedv temperature, preferably at the boilingpoint of the solution.. The alumina thus produced then can be optionallytreated with an alkaline reagent, eg., ammonium hydroxide. Anothermethod for preparing alumina is to precipitate alumina gel from analuminum salt, eg., aluminum chloride, aluminum sulfate, aluminumnitrate, etc., by means of an alkaline reagent, e.g., ammoniumhydroxide.

The precipitation is conductedv at a pH of. between about.

3.5 to 7. The gel thus produced can then be further treatedwithanalkaliue reagent,.e.g., ammonium hydroxide, with or. without aging fora suitable periodof time. In all of the preparations of alumina givenabove, it is also intended-that-the alumina may be aged, with or with-.out treatment by means of an alkaline ,.reagentfor a period of at leastabout hours, more usuallyat.least about 17 hours. The aluminaprepared bythe methods described above will be either gammaforr eta-alumina ormixtures of the two.

In the preparation of the catalyst, various techniques can be used. Thehetcropoly acid can be iirst prepared in accordance withv the methodsknown to those. skilled inthe art. The heteropoly acid can be dissolvedin water and/or an aliphatic alcohol, eg., methanol, ethanol, butanol,pentauol, etc., and used as a solution for the purpose of mixing withthe carrier material. The carrier material canbe inthe hydrous, driedand/or. calcined form prior toV admixture with the heteropoly acid. Thesolid heteropoly acid can bemixed directly with the carrier material,which may or may .not contain suicientwater and/or aliphatic alcohol todissolve and thus. dispersethe heteropoly. acid, and. in the eventthereis insufficient. solvent, it can be added toelect such a purpose. The pHof the nal. mixture may be on the acidic vor basic. side, provided thecatalyst after nal treatment, such .as calcination, is acidic.Accordingly, prior to calcination, the catalyst may have a pH of about0.5 to 12. The catalyst mixture after thorough mixing is subjected toardrying. operation at a temperature not greater than about 400 F., moreusually, about.150 to about 250 F., for a period of about 6 to about 50hours, more usually, about 10 to about 30Yhours. Following dryingit iscalci'nedv at a temperature not greater than about 400 F., more usually,about 600 to about 1250 F. In some cases, temperatures as high as 1500F. may be used, howeven, care should be taken to avoid `decomposing theyheteropoly acid.. The calcination .treatment isaconf; ductedv for aperiod'of about 1 to about20 hours,; mo.reA

usually, about 2 tofabout'S hours..

Having thusv provided a general'v descriptionv of the present invention;referencey will be: had to thev accompauying drawing which illustrates atest unit which was employed for the purpose: of evaluatingl thepresentinvention.

In the 'accompanying drawing, hydrogen was. supplied fromsource 5 andit` passed: to a` rotameter 6'whereinthe ratey of hydrogen. was.-measured. The measured hydio.

In the treatment ofthe alumina` solv gen Howedfrom: the', rotameter to`a. valvedsline; S and thereafter. it passedptoloneof-.tworcircuits,;namely, acirL cuit involving .the removalof oxygenand'water from the hydrogen gas .streamandtherother circuitWhich;bypassed the oxygen .removalz-sy-stemfgoing directly to a wettestgas, meter. Water wasraddedrto Aeither stream of hydrogen gas inthedesiredquantity; Whentit is desired to produce'dr'y hydrogen, thehydrogen lowed'intoline 10 which contained avalve 11 in an openposition.Theprocessng of the hydrogentthrough. the other circuitinvolved .passingthe hydrogen through a line 12 which containedv a valve 14. Thehydrogenfinline 10 .owed into a Deoxo unit lcomprised-'of palladiumon=aluminum oxide wherein oxygen removal was effected. Followingthe.deoxygenation. step in .vessel 16, the. hydrogen passed from. the bottomthereof into a.1ine.18 which. was connected. toi the; bottom. endof .adryer 20 'havingpresenh therein: an,

hydrousycalcium sulfate. for; the removallqofrmoisture in.

the hydrogen gas.; The, driedhydrogen: gas.passed.over.=

. head'fromgdryer. 2l). into an overheadaline .21 and then it wasmeasured by means of a Wettest gas meter 23.. Ay

hydrocarbon; mixturexsimilar, to the charge naphthawas used. in .the wettest meter insteady of4 water. Since the hydrogengas might absorb asmall amount of.water which might bev present inthe hydrecarbonxmixture.in thev gas meter, it was passed through a: line 25 Whichwas-connectedtoa second dryer 26.- containing. anhydrous calcium sulfate for theremoval of water; Thewhydrogen gasstream was. discharged from the topyofk dryer 26 throughv a line 23 which joined withgaline. 29;.. The.deoxygenated gas was then passed throughr1ine-34 tothewater saturator37,. WhereV the desiredv concentration of. water vapor was supplied.Ifno Water was desired, the dryr deoxygenated hydrogen by-passed. thelsaturator throughlinev 42..

In the event thatit was desiredto incorporateanpredetermined quantity ofwater vapor into thehydrogen gas stream, without removing traces ofoxygen beforehand, valve 11 inline'l@ waskept in a closed positionandvalve 14 in line .12 was left open.. In this case,. the measured.hydrogen fromrotarneter y6 was iirst measured' in a high. pressurey wettest gas meter 30.y TheY measured hydrogen gas stream flowed firstthrough line 29 in Whichthere was situated va yalve 32. In this type ofanoperation, valve 32 was maintained ina closed positionand the hydrogengas .streamilowed througha line, 34 in whichthere was installed a valve35 inan open position. The hydrogen. gasstream then passed into the.bottom of.saturato1-37 which containedpwater. andzwas surrounded by.v anelectric jacket to maintain. the, temperature at. a desired level forobtaining the appropriate quantity of water vapor in the hydrogenfgasstream. Thefmoisture laden hydrogen gas passed overhead lfrom saturator37 into aline 39fin which there was installed a valve 40 in an openposition. When a dry gas was employed for the pretreating operation,valves 35 and 40 were maintained closed inorder to avoid moisture fromgetting into the hydrogen gas; Likewise, in such an operation, valve 32vin line 29 was kept open inorder that the hydrogeny gas by-passedsaturator 37 by means of a line 42. Thehydrogen'containinggas thenflowed through a line which was connected to a main header 45 by whichprocessing materials were' charged to the reaction zone containingthecatalytic material.

During the reaction cycle, the oil being processed was supplied fromIanoilfeed tank 50 .throu'gh'a line 51 connected to the bottom thereof .andthencez-transportedby means of pumpy 53' through a line S5 which wasconnected to the main header' 45.v The mixture of lhydrogen containinggas and oil flowed from header 45-into a line 57 which was connected toa coil 5S surrounding the reactor vessel 60. The coilSSI-Waswounddownwardly across the length of the reactor for a coillength.distance of l0 lfeet, and then upwardly across the same area ofthe reactor before entering; the ytop otthereactor as line 62.

The reactor was a cylindrical vessel .having an internal diameter of.1.5 inches and a length of `1.5 feet. The catalytic material, beingpresent in the form of 9&6 inch pellets, occupied 550 cc. of the reactorcapacity. The reactant materials owed downwardly over the catalyticmaterial and thence passed from the reaction zone through a bottom line64 which was connected to a condenser 65. The reaction product passedthrough an internal coil 66 which was surrounded by`cooling waterintroduced via line 68 and then leaving the condenser via line 70. Thecondensed liquid product owed from the bottom of the condenser through aline 72 which was connected to the top of a high pressure receiver 73.Any gaseous material which was combined with the liquid product passedfrom receiver 73 into an overhead line 75 which was. connected to asecondary cooler 76. In the secondary cooler any gaseous material whichwas condensable accumulated therein and was removed from the bottomthereof through a line 79. The normally gaseous material in thesecondary cooler 76 passed overhead through a line 80. The liquidproduct in the high pressure receiver 73 was discharged through thebottom thereof by means of a line 82 and then it combined with theliquid product flowing through line 79 in line 83 in which there wasinstalled a valve 84 for the purpose of maintaining the desired highpressure within receiver 73. The combined liquid product in line 83flowed in to a low pressure receiver 85. The liquid product was thendischarged from receiver 85 through a bottom valved line 87. Any gaseousmaterial which was present with the liquid product was removed from thetop of receiver 85 and it owed through a line 89. The normally gaseousproduct from the secondary cooler 76 is passed through a pressurecontrol valve 92 which is installed in the overhead line 80. Thenormally gaseous products in lines 80 and 89 were combined in line 94before passing through a gas meter 95. The measured gaseous product thenilowed through line 97 before a portion thereof was taken as a gassample through a valved line 98 and the remainder was vented through Ialine 99.

The temperature of the reaction zone was maintained by submerging thereactor with coil 58 into a molten lead bath maintained at a desiredtemperature. The molten lead bath is not shown in the schematic diagram.After the reaction cycle had run for the prescribed period of time, thecatalytic material was regenerated by employing a regeneration gaslconstituting a mixture of.

nitrogen and air. In the case of regeneration at atmospheric pressure,air was introduced through a line 101 and nitrogen was supplied througha line 102, and both of these lines were connected to the main header45, from which the material passed into line 57 prior to flowing throughcoil 58 circumscribing the reaction vessel. Following the reactioncycle, the stream of nitrogen was passed through the reactor in order toremove as much of the reaction product wetting the catalyst as waspossible. This was carried out at a temperature of about 875 to about1050 F. and for a period of 45 minutes. Following the purging cycle, airwas introduced along with the nitrogen in Va quantity appropriate toobtain 2% by volume of oxygen. The temperature of the catalyst duringthis cycle of the operation was maintained at l 1l) 1000 grams of newaluminum pellets, 4000 grams of used aluminum pellets, 10 liters ofdistilled water and 100 cc. of mercury.

A A H.P. Easter mixer with a 6 inch three blade propeller was used foragitation. Glacial acetic acid, Merck reagent, was added continuously(1.3 cc./min.) from a buret, and steam was introduced for 4 minutes asshown in the following table:

Time (min.) CHCO OH pH at C Notes 0 Steam in 4 min. 6. 5

78 5. 9232 C Aluminum very reactive.

The weight of the product obtained was 10,706 grams.

Since an ignition loss gave 95% solids, 1025 grams of4 A1303 werecalculated to be present. The density was 1.047 grams per cc. at 65 C.While stirring, 208 grams of ethyl orthosilicate, Si(C2H50).3, (59.2grams Si03) were added. The pH was 6.12 at 28 C. When 'the stirring wasstopped, the Si(C3H50)4 carne to the surface. Agitation was continuedand 25 cc. of concentrated ammonium hydroxide were added causing theslurry to gel to a solid state. After diluting with 2 liters of water,the pH was 7.52 at 28 C., and the slurry was still thick. Another l0 cc.of NH4OH and 2 liters of water caused the pH to rise to 7.78 at 28 C.Since thel slurry was still thick, the addition of 2 more liters ofwater permitted easier stirring. The pH was 7.60 at 0 32 C. A nal 15 cc.of the base was added, followed about 950 to about 1l00 F. Theconcentration of airV l CATALYST I The following'reactants were chargedto a 20 gallon wooden barrel in the order listed below:

75! the purpose of determining the effectiveness of Catalyst I.

by l liter of water giving a pH of 8.10 at 32 C.

The product was spray dried in the Niro unit at inlet and outlettemperatures of 395 C. and 112 C., respectively. The feed rate was 83cc. per minute, and the atomizer pressure was 5.2 lig/cm?. The weight ofthe spray dried material was 1153 grams. The powder was transferred totwo quartz trays and calcined 6 hours at 1470 F. in both the Cooley andHoskins furnaces. The calcined powder was combined and mixed. The weightwas 601 grams. X-ray reported etaand gamma-Al3O3.

Phospho molybdic acid, H3P04l2Mo03XH3O, was prepared according to theprocedure of Linz, I. and E.. Ch., Anal. Ed. 15, 459 (1952). Exactly1992 grams of the vacuum dried product were obtained. An analysis gave1.4% P, 55.6% Mo. The atomic ratio of outer acid forming element tocentral acid forming element was 12.07, and the equivalent weight was597.

Five hundred grams of the calcined powder placed in an evaporating dishwere impregnated with 59.5 grams of H3PO4-12Mo03-XH3O, (49.5 gramsM003), dissolved in 1 liter of water. The solution which had beenheated, was cloudy and yellow. An' additional 140 cc. of water were usedto Wet the alumina thoroughly. The catalyst was placed in the Elconapoven where it remained for 23 hours at 225 F.

The material dried into a large, soft, white cake which was easilypowdered. It was passed through a 20 mesh" screen to remove soft lumps,and transferred to a quartz tray and calcined 3 hours at l000 F. in theHoskins furnace. White pills, measuring 1%@ inch in diameter,. wereprepared, and a 550` cc. test unit charge weighed 291 grams. A chemicalanalysis of the nished catalyst" gave 8.95% M003, 4.52% Si03, 0.15% Pand X-ray reported etaand gamma-A1303.

Another catalyst was employed in this evaluation, for

1l on a comparative-basis, andthis catalyst'is designated as No. ll..Catalyst ILwas prepared by conventional means and it contained: 9.3% ofM003, 3.6% of S102, 0.4% chloride ion and the remainder is'alumina.

The feed stocks evaluated by means of this invention are given in TableI below.

Table l Feed Designation A B C D API Gravity 51. 3 52. 8 52. 2 53. 1ASTM Distillatiou, F'

IBP. 236 239 228 216 267 283l 240 234 275 293 242 241 291 298 248 250303 309 255 260 315 310 262 274 326 323 271 200 338 330 282 308 349 337295 324 364 346 312 343 385 360 336 366 404 373 355 382 E.P 426 387 385412 Reid Vapor Pressure, p.s.i 0. 58 0. 55 22 0. 68' K-CharacterlzationFactor 11.89 11. 99 11.71 1lA 84 Refractive Index, 710ML.-- 1. 4239Aniline Point, F 140 134 129 127 Octane No. CFRR clear 27.6 25. 9 45. 145.1- AromaticsJol. percent (ASTM) 9. 14.9 11. 5 8.9 Oletins, Molpercent 1.0 1.1 1. ,7 10.0 Sulfur, Wt. percent- 0.05 0.104 0. 06 0.14Molecular Weight. 134 135 117 123 In. the following experiments, theytest unit described in. the drawing was brought on stream, followingregeneration, in the following manner:

(a) The catalyst was regenerated with air and nitrogen at 950 F.

(b) The catalyst was flushed with air `for 30 minutes 12 catalystonfourdiffe'rent feed stocks. By thesecomparisons, it is clear that ahetei'opoly, acid isunexpectedly superior over a molybdena: catalystregardlessv of the type ofi feed stockA used.. This. is':.evidentlfronisthelzyieldsmrel portedv at a 95 CFRR@clearrratiiig.;v During .theinitialv runs: which utilized fresh.- catalyst the .catalyst did Ynotshow high activity 'until it was employed under reaction conditionsl forseveral hours.

Hai/ing thusdescribed thev .present invention'by refer-v ece to specificexamplesthereoiit should be understood that no undue limitations orrestrictions .should be irn. posedbyreason thereof, but that'.thezscepeof .the inven-`v tion. is deiined bythe .appended vclaims'.-

I claim:

l. A processwwhichA comprisesxtreatinga Yheteropoly acid catalyst with ahydrogen containingA gas, in the presence of about 0.1-to about l molpercent of water based. on the quantity of'hydrogen, .at .atemperature'o about 750 toaboiit 1200 F.,..and thereaftercontact-- ingthe treated-catalysttwith a lighthydrocarbouoil,in'

the presence of about 0.50 to about 2.5 mol vpercent of water, and undersuitable' reforming' conditions.

2. A process which comprises treating a heteropoly acid catalyst withahydrogen containing. gas, inrthe presence of about 0.5` to about 6 molpercent kof water based on the quantity of hydrogen, at a temperature ofabout 875 to about 1l00 F., and thereafter contactingthe treatedvcatalyst with a light hydrocarbon oil, in the presence of. about 0.50 toabout 2.5 molpercent of..water, and under suitable reforming conditions.

3. A process which comprises treating a heteropoly acid catalyst with ahydrogen. containinggas, in the presence of about 0.5 to about 6 molpercent of added .water based on. the quantity of hydrogen, at atemperature of at 1050() F' and atmospheric pressure' 35 875 to about1l00 F and thereafter ContactinU the (c) The catal st'bed was flushedwith nitrogen for 15 a t s 81940., 5% and atmospheric pressre c treatedcatalyst with a light hydrocarbon oil, in the presminu e (d) Hydrogencontaining 0.5 mol percent. of Water lrjtgufobltagg Stomsuetrclocfgattta was introduced at atmospheric pressure and at the' rate p L of 30standard cubic feet per hour. The pressure was 4() pebslfre of 25 tozbout 100G p'sl'g" il Weight Space. velocity of about 0.3v to about 10,and in the presence allowed to build up to 250 p.s.i.g. and it tookabout 3 dd d d l t, f b t ,O0 b It minutes to elect this pressure level.During this stage, 30.3006 [fiyb rogen m me amoun o a ou J t0 a 0L thetemperature of the catalyst bed increased. S'C' (e) A static pressure of250 p.s.i.g. of wet hydrogen 4A Proess for mcrfiasmg the Yleld 0f hqulqProduCt was maintained for 30 minutes c 45 of high anti-knock qualityproduced in a reforming treat- (f) The hydrogen containing 0.5 molpercento Water nerit of ai hgit hilcroclbon Olllwhlcil Comprlses con;was-passed over the catalyst at the rate of 11.0 standard aftmg Sad 011,Wlt a etefQPO Y .acld Catalyst und Cubic feetvper homfolminutessuitablereforming conditions including added hydrogen Steps (d), (e) and (j)were conductedzat a tempel-a.- and in the presence Vof about 0.1 .toabout l5 mole perture'of about 930 F. on the average. 50 cent of waterbased on the quantityof added hydrogen. (g) Oil was charged with wethydrogen flowing to the 5. The process in claim 4 in which the centralacid reactor. forming element of the heteropoly acid catalyst is molyb-The. data obtained in the test unit is reported in Table denum. y IIbelow. 6. The process in clairn`4 in which the central acid Table II 1 23 4 5 6 7 s Run No I 1r r Ir r ir r 1r Y, Feed A A B B o C D D OperatingConditions: F 93o 930 930 93o 930 950 900 900 giigierrtgiig 250 250 25025o 250 250 250 250 space Veiocity, Wohin/W... 1.0 0. 5 o. 5 0. 5 1.0 1.0 1. 0 o. s H2 rare, s.e.f.b 5, 000 5,000 5, 000 5. 000 5, 000 5, 000 5,000 5,1000 on Rate, gm./hr 244 270 122 270 244 540 24 432V Cataiyst, ams244 540 244 540 244 5,40 244 540 Mol Percent H2O (basis 112).- 0. 5 0. 50. 5 0. 5 0. 5 0. 5 0. 5 0. .i YI lergdifrnli, lis) 2 2 2 2 2 2 2 S52' ve Lsicfuiii ivjiid (a100% Ci) Vol. Percentse. 1 s3. 1 s4. 9 sv. 5 88,188.4 87.0 92.3 CifreeL'iquid, voi. Percent 81.2 72.7 80.6 80.2 80.982.4. 82.4V 59.1 Butanes, Vol Percent; 4.9 10.4 4.3 7.3 7.2 6.0 5,2.3,2. Dry oas, Wt. Percent. 11.5 15.8 13.1 11. 6 10.4 9.6 10.4 0.2InspectionszN Y CFRR lar C free Olslgiinel e 4 95. 2 95. 4 97. 9 90. 097. 3 90. 2 92. 6 75. 5

' N. Yitllitlaietiiigslf.. 81.4 73.2 83.0 71.0 82.9 77.7 80.2 73.2

In.Table-.II above,. `four comparisonsV are made, between. aS-heteropolyacid catalystand molybdenum oxide forming element .of the heteropolyacid catalyst is chromium.

7. The process in claim 4 in which the central acid forming element ofthe heteropoly acid catalyst is vanadium.

8. The process in claim 4 in which the central acid forming element ofthe heteropoly acid catalyst is tungsten.

9. The process in claim 4 in which the outer acid 4forming element ofthe heteropoly acid catalyst is selected from the group consisting ofphosphorus, germanium, tellurium, arsenic, alumina, boron, silica,manganese, iron, cobalt, rhodium, chromium, selenium, iodine, platinumand antimony.

10. The process in claim 4 in which the central acid forming element ofthe heteropoly acid catalyst is molybdenum and the outer acid formingelement is phosphorus.

11. A process for increasing the yield of liquid product of highanti-knock quality in a reforming treatment of a naphtha fraction whichcomprises contacting said naphtha fraction with phosphomolybdic acidunder suitable reforming conditions including added hydrogen and in thepresence of about 0.1 to about 15 mole percent of Water based on thequantity of added hydrogen.

12. A process for increasing the yield of liquid product of highanti-knock quality produced in a reforming treatment of a lighthydrocarbon oil which comprises contacting said oil with a heteropolyacid catalyst under suitable reforming conditions including addedhydrogen and about 0.1 to about 10 mol percent of Water based on thequantity of added hydrogen.

13. A process for increasing the yield of liquid product of highanti-knock quality produced in a reforming treatment of a lighthydrocarbon oil which comprises contacting said oil with a heteropolyacid catalyst under suitable reforming conditions including addedhydrogen and about 0.25 to about 5 mol percent of water based on thequantity of added hydrogen.

14. A process for increasing the yield of liquid product of highanti-knock quality produced in a reforming treatment of a lighthydrocarbon oil which comprises contacting said oil with a heteropolyacid catalyst under suitable reforming conditions including addedhydrogen and about 0.5 to about 2.5 mol percent of water based on thequantity of added hydrogen.

15. A process for increasing the yield of liquid prodruct of highanti-knock quality produced in a reforming treatment of a lighthydrocarbon oil which comprises pretreating a heteropoly acid catalystwith hydrogen containing between about 0.1 and about 15 mol percentWater at a temperature between about 750 F. and 1200 F. for a period ofbetween about 0.05 and about hours and contacting said light hydrocarbonoil with said pretreated catalyst under suitable reforming conditions,including added hydrogen and in the presence of between 14 about 0.1 andabout 10 mole percent of water based on the quantity of added hydrogen.

16. The process in claim 15 in which the central acid forming element ofthe heteropoly acid catalyst is chromium.

17. The process in claim 15 in which the central acid forming element ofthe heteropoly acid catalyst is tungsten.

18. The process in claim 15 in which the outer acid forming element ofheteropoly acid catalyst is selected from the group consisting ofphosphorus, germanium, tellurium, arsenic, alumina, boron, silicagmanganese, cobalt, iron, rhodium, chromium, selenium, iodine, platinumand antimony.

19. The process in claim 15 in which the central acid v forming elementof the heteropoly acid catalyst` is molybdenum and the outer acidforming element is phosphorus.

20. A process for increasing the yield of liquid product of highanti-knock quality in a reforming treatment of a naphtha fraction whichcomprises pretreating a phosphomolybdic acid catalyst with hydrogencontaining between about 0.1 and about 15 mol percent water at a.temperature between about 750 F. and 1200 F. for a period of betweenabout 0.05 and about 10 hours and contacting said naphtha fraction withsaid pretreated catalyst under suitable reforming conditions, includingadded hydrogen and about 0.25 to about 5 mol percent of water based onthe quantity of added hydrogen.

21. A process which comprises contacting a light hydrocarbon oil with aheteropoly acid catalyst, in the presence of about 0.1 to about 15 molepercent of water, and under suitable reforming conditions.

22. A process which comprises contacting a light hydrocarbon oil with aheteropoly acid catalyst, in the presence of about 0.1 to about 10 molepercent of Water, and under suitable reforming conditions.

23. A process which comprises contacting a light hydrocarbon oil with aheteropoly acid catalyst, in the presence of about 0.25 to about 5 molepercent of Water, and under suitable reforming conditions.

References Cited in the le of this patent UNITED STATES PATENTS2,131,089 Beek et al. Sept. 27, 1938 2,433,603 Danner et al. Dec. 30,1947 2,547,380 Fleck Apr. 3, 1951 2,608,534 Fleck Aug. 26, 19522,642,383 Berger et al. June 16, 1953 2,642,385 Berger et al June 16,1953 2,661,320 Beckberger et al Dec. 1, 1953 2,768,933 Burton et al.Oct. 30, 1956

3. A PROCESS WHICH COMPRISES TREATING A HETEROPOLY ACID CATALYST WITH AHYDROGEN CONTAINING GAS, IN THE PRESENCE OF ABOUT 0.5 TO ABOUT 6 MOLPERCENT OF ADDED WATER BASED ON THE QUANTITY OF HYDROGEN, AT ATEMPERATURE OF 875* TO ABOUT 1100* F., AND THEREAFTER CONTACTING THETREATED CATALYST WITH A LIGHT HYDROCARBON OIL, IN THE PRESENCE OF ABOUT0.2 TO ABOUT 5 MOL PERCENT OF WATER, AT A